Plastics and methods of making same.



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WILLIAM T. BONNER, OF WASHINGTdN, NORTH CAROLINA, ASSIGNOR OI! ONE-HALF TO K. P. McELBOY .AND ROY F. STEWARD, BOTH' OF WASHINGTON, DISTRICT OF COLUMBIA, AND MITFORD C. MASSIE, OF NEW YORK, N. Y.

PLASTICS AND METHODS OF MAKING SAME.

No Drawing.

pounds of like type upon cellulose and simi-v lar carbohydrates; and it also comprises a process of forming valuable derivatives from carbohydrates, said process comprising a method in which the carbohydrate is molec'ularly altered to form new bodies by the action of ammonia or like bodies, such new bodies being in a reactive form adapting them to the formation of carbohydrate esters and also comprising a method of' forming such esters and products comprising the same, all as more fully hereinafter set forth and as claimed.

I have discovered that by treating cellulose and like carbohydrates with dry, am-

l' monia; (NIL), the materiaLpniteswith the ammonia and undergoes a profound'molecu lar alteration though still retaining the general carbohydrate properties, and among them the valuable filmand filament-forming properties, becoming much more reactive and becoming well adapted as a material for producing esters having valuable properties, such as, for instance, the sulfo carbonate. For instance, if I take ordinary paperpulp or other forms, of commercial cellulose, dry it to free it of mechanically held, or adsorbed, moisture, and then immerse it in liqu'id; dry ammonia a reaction at oncesets in with evolution of heat. In practice Ijprefer to perform this reaction under coolin conditions to avoid far-going changesbvheniseeking to producethe specific products more. specifically hereinafter ,described..-, The materials may, for instance, be brought into reaction in apparatus surrounded by a. cooling liquid maintained around zero Fahrenheit. After'a time when the cellulose has undergone the changes desired,-I remove the liquid ammonia andsubject the altered cellulose to a vacuum. This removes substantially all the ammonia me- Specification of Letters Patent.

scribed.

Patented Feb. 29, 1916.

Application filed May 2b, 1908. Serial No. 433,872.

chanically held as gas, and leaves my altered cellulose as a light dry powder, the fibers being generally found to be broken down to an impalpable powder. As to the chemical nature of the action which takes place in treating the carbohydrate with the 'NH,, I am not at present aware and content myself with noting the observed facts.

The lightdry powder resulting from the action of the NH upon cellulose to the extent indicated and in the way described, is a cellulose derivative in an extremely reactive form. It should as a rule be employed while quite fresh and pending such use should be kept cool and dry and under exclusion of air to prevent loss'of reactivity. It is possessed of properties which well adapt itto the formation of such esters as ,ment with the correspondin acids, anhydrids or acidyl chlorids. Ifpon treatment with very strong acetic acid, for instance, it yields useful products. :It may be nitrated bynitric acid and yarious nitrating mixtures. It is particularly well adapted fortreatment with carbon disulfid however, and such treatment and resulting products will be more specifically hereinafter de- My invention however, broadly stated, comprises this new and useful body and the and reacting upon it by, various ester-forming substances as well as the process of producing it and its derivatives Upon contacting this powder with carbon disulfid, either as liquid or vapor, it reacts therewith to form a light. dry, yellowish powder of a fairly permanent nature, though best preserved in a cool dry state under exclusion of derivatives produced by combining it with,

fixed alkali, soluble salts .orother mineral matter except the natural ash constituents of thecellulose employed; an amount of mineral matter insignificant for all practical purposes and of a character wholly harmless. Upon treating this yellowish product with the proper amount of Water, it dissolves to form a thick, viscid solution, useful formany plastic purposes. The dry product when well made being homogeneous, the solution is likewise homogeneous, therebydiffering from the ordinary carbon di-I sulfid compounds of cellulose. It differs also in many other respects; notably in the absence of fixed mineral matter in solution. Ordinary viscose being, to state its composition empirically, a compound of caustic soda, cellulose and carbon bisulfid, is heavily alkaline. and when the cellulose is recovered, the soda remains therein as an impurity which must be carefully washed out; an operation attended with someditficulty and leaving the cellulose porous and hygroscopic. Naturally if the soda be not thoroughly extracted, as frequently happens, the cellulose is quite hygroscopic.

The cellulose-carbon disulfid compound of the present invention upon beingdissolved in water yields a neutral solution, the compound itself being neutral. This solution upon being heated gives recovered cellulose in a hard, tough form well adapted for plastic purposes; yielding films, filaments or substantial masses according to conditions. If the solution prior to heating be used to form a stiff, plastic'mass by incorporation of neutral, indifferent mineral matters as fillers, such as Whiting, zincoxid, etc., the recovered cellulose binds these fillers into tough, strong masses of the shape of -the containingvessel or mold. All the constituents of the solution other than the cellulose being'volatile, upon drying such masses a' finished product is obtained directly, 'gno washing being necessary. f

- From the solution formed as described,

cellulose may be regained or recovered by acidulation with various acids. by treating with various basic oxids and by the ordinary reagents for salting out colloid bodies. The cellulose compound in the solution not being very stable, these precipitates furnish to heat in a drving recovered cellulose upon aging.

Heating and drying may'usefully be combined into a single operation, the solution with or without fillers, being simply exposed chamber. When it is desired to produce a cellulose filament or. film, as in making thread or in waterproofmg cloth, this operation is particularly useful. In insulating wire, for example, the wire may be continuously led through a bathof'the solution, thence through a steam chamber and thence into a drying chamber. In going through the bath it becomes covrequired, the dried wire may be directly coiled on the magnets or armatures. The covering is neither'porous nor hygroscopic. Cloth may be treated in much the same man er, a strip of cloth having the solution applied to one side, or being impregnated therewith, steamed and dried. Articles may be given a hard, tough, non-porous, permanent varnish of cellulose by dipping, steaming and drying. A simple drying in lieu of steaming and drying may be employed.

When desired, the original solution may be mixed with other colloid bodies, such as casein, glue, gelatin, etc., or with ,-hygro-. scopic, softening bodies, such as glycerin. The solution being free of corrosive, fixed alkalis like soda or potash, does not injuriouslv react on casein, gelatin, etc.

Filaments may be made from the solution by squirting it through suitable jet nozzles into acid baths, anil-in bath-s, drying chambers, steam chambers, etc. The filamentsdo not require the washing necessary with most other artificial filaments.

Cloth impregnated with the solution and afterward dried, gives a. good article of imitation leather. Other colloids may be simultaneously employed if desired. Leather itself may be waterproofed and filled with recovered cellulose by the aid of the described solution. The solution being free from caustic alkalis does not iniuriously affect wool, leather and other animal fibrous materials. Y

Masses of cellulose recovered from the pure solution take ,theshape of the containins.) .sel and form hard; solid, tough bodies which av be turned, drilled and otherwise worked like horn; They are non-porous and. require no washing. Other, carbohydrates than cellulose may be treated in the same manner with results which are analogous though not identical. Woods and other vegetable materials may. also be treated in the same manner.

, Any suitable apparatus may be employed for any 'of the described operations. In treating the cellulose with ammonia, it is preferable .to use enameled vessels to ,pre- 7 and to prevent the reaction going for another treatment of fresh cellulose. The chief purpose in using the liquid ammonia is to have a large excess of NH relative to the cellulose as this facilitates and quickens the action. Gaseous ammonia requires larger vessels and is slower in its action unless temperatures be raised. The. preliminary drying of the cellulose is quite desirable, and may beefi'ected in any suitable manner and with any suitable apparatus. Drying at or near the temperature of boiling water (212 F.) for, say, half an'hour, is suflicient. Any commercial form offcellulo se may be employed, such as cotton, paper or ordinary wood paper pulp. The wood paper pulp is quite suitable.

The intermediate product resulting from the action of the ammonia on the cellulose may be kept, sold or used directly. The dry, yellow compound of carbon bisulfid with this product may similarly be kept, sold or used directly. Being dry, it is convenient to package and transport, and it may be employed to produce the described solution at the place of use. But, as stated,- when either is to be preserved, it should be kept cool, dry and away from the action of am In lieu of ammonia, other anhydrous nitrogen compounds of the NH type, such as anilin, methylamin, ethylamin, dimethyl-' amin, trimethylamin, and the like, may be employed.

What I claim is 1. As a new composition of matter, a water solution of a compound of carbon disulfid with a product resulting from the treatment of a carbohydrate with ananhyr drous nitrogen compound of the NH type, said solution being neutral, coagulable and free of fixedmineralmatter.

2. As a new composition of matter, 'a water solution of a compound of carbon disulfid with a product resulting from the treatment of cellulose with NH said solution being neutral, coagulable and free of fixed mineral matter. v

3. In the manufacture of plastic compositions, the process which comprises treating dry cellulose with an anhydrous nitrogen compound of the NH type. 4. In the manufacture of plastic compositions, the process which comprises treating a dry carbohydrate with an-anhydrous nitrogen compound of the NH, type.

5. In the manufacture of plastic compositions, the process which comprises treating a dry carbohydrate with NH see 6. In the manufacture of plastic compositions, the process which comprises treating a dry cellulose with NH 7 Inthe manufacture of plastic compositions, the process which comprises treating cellulose with liquid NH 8. The process of forming plastic compositions which comprises treating a carbohydrate with NH and subsequently treating the product with an ester-forming body;

9. The process of forming plastic compo-- sitgons which comprises treating cellulose w h 'NH, and subsequently treating the product with an-ester-forming body.

10. The process of forming plastic com p ositions which comprises treating a carboh/ydratewith NH and subsequently treating the product with carbon disulfid.

11. The process of forming plastic compositions which comprises treating cellulose witlf NH, and subsequently treating the product with carbon disulfid.

12. The process of forming plastic compositions which comprises treating dry cellulose with anhydrous ammonia, treating the product of this action with carbon disulfid and dissolving in waterthe product so obtained.

13. The process of forming plastic compositions which comprises treating dry cellulose with liquid anhydrous ammonia,

treating the product of this action with carbon disulfid and dissolving in water the product so obtained.

14. The process of forming plastic compositions which comprises treating dry cellulose with liquid anhydrous ammonia under cooling conditions, removing the excess of liquid, removing adhering ammonia by vacuum and treating the product with carbon disulfid.

15. The process of forming a plastic composition which comprises treating dry cellulose with liquid anhydrous ammonia under cooling conditions, removing the excess of ammonia, treating with carbon disulfied and dissolving the resultant compound in water.

16. As a new composition of matter, a material comprising the product of reaction of cellulose, anhydrous ammonia and an ester-forming body.

In testimony whereof I afiix my signature, in presence of two witnesses.-

WILLIAM T. BONNER.

Witnesses:

PHILIP T. LARNER, ALFRED M. 'I-IoUGH'roN. 

